U.S. patent application number 13/649634 was filed with the patent office on 2013-04-25 for electroconductive polymer suspension and method for producing the same, electroconductive polymer material, and solid electrolytic capacitor and method for producing the same.
This patent application is currently assigned to NEC Tokin Corporation. The applicant listed for this patent is NEC Tokin Corporation. Invention is credited to Tomoki Nobuta, Yasuhisha Sugawara, Satoshi SUZUKI, Yasuhiro Tomioka.
Application Number | 20130100585 13/649634 |
Document ID | / |
Family ID | 47990838 |
Filed Date | 2013-04-25 |
United States Patent
Application |
20130100585 |
Kind Code |
A1 |
SUZUKI; Satoshi ; et
al. |
April 25, 2013 |
ELECTROCONDUCTIVE POLYMER SUSPENSION AND METHOD FOR PRODUCING THE
SAME, ELECTROCONDUCTIVE POLYMER MATERIAL, AND SOLID ELECTROLYTIC
CAPACITOR AND METHOD FOR PRODUCING THE SAME
Abstract
The present invention provides an electroconductive polymer
suspension for providing an electroconductive polymer material with
a high electroconductivity and a method for producing the same, and
particularly provides a solid electrolytic capacitor with a low ESR
and a method for producing the same. It includes a first step of
carrying out chemical oxidative polymerization of a monomer
providing an electroconductive polymer by using an oxidant in a
solvent containing a first dopant including an organic acid or a
salt thereof to synthesize an electroconductive polymer; a second
step of purifying the electroconductive polymer; a third step of
adding a second dopant, mixing an oxidant, subsequently adding a
third dopant, and further mixing an oxidant in an aqueous solvent
containing the purified electroconductive polymer; and a fourth
step of carrying out an ion-exchange treatment to the mixture
liquid obtained by the third step to obtain an electroconductive
polymer suspension.
Inventors: |
SUZUKI; Satoshi;
(Sendai-shi, JP) ; Nobuta; Tomoki; (Sendai-shi,
JP) ; Sugawara; Yasuhisha; (Sendai-shi, JP) ;
Tomioka; Yasuhiro; (Sendai-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NEC Tokin Corporation; |
Sendai-shi |
|
JP |
|
|
Assignee: |
NEC Tokin Corporation
Sendai-shi
JP
|
Family ID: |
47990838 |
Appl. No.: |
13/649634 |
Filed: |
October 11, 2012 |
Current U.S.
Class: |
361/525 ;
252/62.2; 427/487; 427/80 |
Current CPC
Class: |
C08G 61/124 20130101;
C08L 65/00 20130101; C08G 73/0266 20130101; H01G 9/028 20130101;
C08L 79/02 20130101; C08G 61/126 20130101; C08L 65/00 20130101;
H01G 9/0032 20130101; H01G 9/025 20130101; C08L 79/02 20130101;
C08G 2261/90 20130101; C08G 2261/51 20130101; C08G 2261/3223
20130101; C08L 25/18 20130101; H01G 9/15 20130101; C08G 2261/3221
20130101; C08L 25/18 20130101 |
Class at
Publication: |
361/525 ;
252/62.2; 427/80; 427/487 |
International
Class: |
H01G 9/025 20060101
H01G009/025; H01G 9/00 20060101 H01G009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 14, 2011 |
JP |
2011-226381 |
Claims
1. A method for producing an electroconductive polymer suspension,
comprising: a first step of carrying out chemical oxidative
polymerization of a monomer providing an electroconductive polymer
by using an oxidant in a solvent comprising a first dopant
comprising an organic acid or a salt thereof to synthesize an
electroconductive polymer; a second step of purifying the
electroconductive polymer; a third step of adding a second dopant,
mixing an oxidant, subsequently adding a third dopant, and further
mixing an oxidant in an aqueous solvent comprising the purified
electroconductive polymer; and a fourth step of carrying out an
ion-exchange treatment to the mixture liquid obtained by the third
step to obtain an electroconductive polymer suspension.
2. The method for producing an electroconductive polymer suspension
according to claim 1, wherein the monomer is at least one kind
selected from pyrrole, thiophene, aniline, and derivatives
thereof.
3. The method for producing an electroconductive polymer suspension
according to claim 2, wherein the monomer is
3,4-ethylenedioxythiophene.
4. The method for producing an electroconductive polymer suspension
according to claim 1, wherein the first dopant and/or the second
dopant are at least one kind selected from a polysulfonic acid or a
salt thereof.
5. The method for producing an electroconductive polymer suspension
according to claim 4, wherein the polysulfonic acid or the salt
thereof is a polystyrene sulfonic acid.
6. The method for producing an electroconductive polymer suspension
according to claim 1, wherein the third dopant is at least one kind
selected from an organic acid with a low molecular weight or a salt
thereof.
7. The method for producing an electroconductive polymer suspension
according to claim 6, wherein the organic acid with a low molecular
weight or the salt thereof is at least one kind selected from alkyl
sulfonic acids, benzenesulfonic acid, naphthalenesulfonic acid,
anthraquinonesulfonic acid, camphorsulfonic acid and derivatives
thereof and iron (Ill) salts thereof.
8. The method for producing an electroconductive polymer suspension
according to claim 1, comprising a fifth step of mixing at least
one kind selected from erythritol and pentaerythritol after the
fourth step.
9. An electroconductive polymer suspension obtained by the method
according to claim 1.
10. An electroconductive polymer material obtained by removing the
solvent from the electroconductive polymer suspension according to
claim 9.
11. A solid electrolytic capacitor which comprises a solid
electrolyte layer comprising the electroconductive polymer material
according to claim 10.
12. The solid electrolytic capacitor according to claim 11,
comprising an anode conductor comprising a valve action metal and a
dielectric layer formed on a surface of the anode conductor,
wherein the solid electrolyte layer is formed on the dielectric
layer.
13. The solid electrolytic capacitor according to claim 11, wherein
the solid electrolyte layer comprises a first solid electrolyte
layer formed on the dielectric layer and a second solid electrolyte
layer formed on the first solid electrolyte layer.
14. The solid electrolytic capacitor according to claim 12, wherein
the valve action metal is at least one kind selected from aluminum,
tantalum and niobium.
15. A method for producing a solid electrolytic capacitor,
comprising: forming a dielectric layer on a surface of an anode
conductor comprising a valve action metal; and carrying out
application or impregnation of the electroconductive polymer
suspension according to claim 9 on the dielectric layer and
removing the solvent from the electroconductive polymer suspension
to form a solid electrolyte layer comprising an electroconductive
polymer material.
16. A method for producing a solid electrolytic capacitor,
comprising: forming a dielectric layer on a surface of an anode
conductor comprising a valve action metal; carrying out chemical
oxidative polymerization or electropolymerization of a monomer
providing an electroconductive polymer on the dielectric layer to
form a first solid electrolyte layer comprising the
electroconductive polymer; and carrying out application or
impregnation of the electroconductive polymer suspension according
to claim 9 on the first solid electrolyte layer and removing the
solvent from the electroconductive polymer suspension to form a
second solid electrolyte layer.
17. The method for producing a solid electrolytic capacitor
according to claim 16, wherein the electroconductive polymer
comprised in the first solid electrolyte layer is a polymer
obtained by chemical oxidative polymerization or
electropolymerization of at least one kind selected from pyrrole,
thiophene, 3,4-ethylenedioxythiophene, aniline, and derivatives
thereof as the monomer.
18. The method for producing a solid electrolytic capacitor
according to claim 15, wherein the valve action metal is at least
one kind selected from aluminum, tantalum and niobium.
Description
[0001] This application is based upon and claims the benefit of
priority from Japanese patent application No. 2011-226381, filed on
Oct. 14, 2011, the disclosure of which is incorporated herein in
its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an electroconductive
polymer suspension and a method for producing the same, an
electroconductive polymer material, and a solid electrolytic
capacitor and a method for producing the same.
[0004] 2. Description of the Related Art
[0005] Electroconductive organic materials are used for an
electrode of a condenser, an electrode of a dye-sensitized solar
cell or an organic thin film solar cell, and an electrode of an
electroluminescence display. As these electroconductive organic
materials, electroconductive polymers obtained by polymerizing
pyrrole, thiophene, aniline or the like are known.
[0006] These electroconductive polymers are generally provided as a
suspension (dispersion) or a solution in an aqueous solvent, or as
a solution in an organic solvent, and the solvent is removed at the
time of use and is used as an electroconductive polymer material.
However, even if the kind of the electroconductive polymer is the
same, since the property of the electroconductive polymer material
obtained is different depending on the condition of the dispersion,
methods for producing a dispersion are variously studied.
[0007] JP 2010-40776 A discloses a technology regarding a
suspension (dispersion) of a polythiophene and a method for
producing the same. The dispersion of a polythiophene contains
water or a mixture of a water-miscible organic solvent with water
as a dispersing medium, a polythiophene consisting of a structural
unit of 3,4-ethylenedioxythiophene, and a polyanion derived from a
polystyrene sulfonic acid with a molecular weight in a range of
2000 to 500000. And, the polythiophene was obtained by chemical
oxidative polymerization in a presence of the polyanion derived
from a polystyrene sulfonic acid with a molecular weight in a range
of 2000 to 500000. It is assumed that an electroconductive polymer
film can be formed by the method.
[0008] JP 2006-228679 A discloses a technology regarding an
electroconductive polymer composition and a solid electrolytic
capacitor using the same. It contains naphthalenesulfonic acid as
an additive which is added to a cationic polymer consisting of
repetitive structural units of 3,4-ethylenedioxythiophene and an
electroconductive polymer obtained by using a polystyrene sulfonic
acid as an anion. It is assumed that an electroconductive polymer
coating film with keeping low specific resistivity can be obtained
by the technology.
[0009] However, like the technology described in JP 2010-40776 A,
the method by chemical oxidative polymerization of
3,4-ethylenedioxythiophene in a presence of a polyanion makes it
difficult to improve the dope rate. Also, like the technology
described in JP 2006-228679 A, the method in which
naphthalenesulfonic acid is added as an additive to an
electroconductive polymer obtained by using a polystyrene sulfonic
acid as an anion also makes it difficult to improve the dope rate.
That is, there was a problem that a polyanion that is an undoped
polyanion which does not contribute to the electroconductivity
excessively exists and that it is not adequate as a technology to
obtain an electroconductive polymer material with a higher
electroconductivity.
[0010] Thus, the object of the present invention is to provide an
electroconductive polymer suspension for providing an
electroconductive polymer material with a high electroconductivity
and a method for producing the same, and particularly provides a
solid electrolytic capacitor with a low equivalent series
resistance (low ESR) and a method for producing the same.
SUMMARY OF THE INVENTION
[0011] The method for producing an electroconductive polymer
suspension of the present invention includes:
[0012] a first step of carrying out a chemical oxidative
polymerization of a monomer providing an electroconductive polymer
by using an oxidant in a solvent containing a first dopant
including an organic acid or a salt thereof to synthesize an
electroconductive polymer;
[0013] a second step of purifying the electroconductive
polymer;
[0014] a third step of adding a second dopant, mixing an oxidant,
subsequently adding a third dopant, and further mixing an oxidant
in an aqueous solvent containing the purified electroconductive
polymer; and
[0015] a fourth step of carrying out an ion-exchange treatment to
the mixture liquid obtained by the third step to obtain an
electroconductive polymer suspension.
[0016] Also, the monomer is preferably at least one kind selected
from pyrrole, thiophene, aniline, and derivatives thereof, and is
particularly preferably 3,4-ethylenedioxythiophene.
[0017] Also, the first dopant and/or the second dopant are
preferably at least one kind selected from a polysulfonic acid or a
salt thereof, and are particularly preferably a polystyrene
sulfonic acid.
[0018] Also, the third dopant is preferably at least one kind
selected from an organic acid with a low molecular weight or a salt
thereof, and is particularly preferably at least one kind selected
from alkyl sulfonic acids, benzenesulfonic acid,
naphthalenesulfonic acid, anthraquinonesulfonic acid,
camphorsulfonic acid and derivatives thereof and iron (Ill) salts
thereof.
[0019] Also, it may include a fifth step of mixing at least one
kind selected from erythritol and pentaerythritol after the fourth
step.
[0020] The electroconductive polymer suspension of the present
invention is obtained by the above-mentioned method. Also, the
electroconductive polymer material of the present invention is
obtained by removing the solvent from the above-mentioned
electroconductive polymer suspension.
[0021] The solid electrolytic capacitor of the present invention
has a solid electrolyte layer containing the above-mentioned
electroconductive polymer material and may have an anode conductor
containing a valve action metal and a dielectric layer formed on a
surface of the anode conductor, wherein the solid electrolyte layer
is formed on the dielectric layer. Also, the solid electrolyte
layer may include a first solid electrolyte layer formed on the
dielectric layer and a second solid electrolyte layer formed on the
first solid electrolyte layer, and the valve action metal may be at
least one kind selected from aluminum, tantalum and niobium.
[0022] The method for producing a solid electrolytic capacitor of
the present invention includes:
[0023] forming a dielectric layer on a surface of an anode
conductor containing a valve action metal; and
[0024] carrying out application or impregnation of the
electroconductive polymer suspension on the dielectric layer and
removing the solvent from the electroconductive polymer suspension
to form a solid electrolyte layer containing an electroconductive
polymer material.
[0025] The method for producing a solid electrolytic capacitor of
the present invention includes:
[0026] forming a dielectric layer on a surface of an anode
conductor containing a valve action metal;
[0027] carrying out a chemical oxidative polymerization or
electropolymerization of a monomer providing an electroconductive
polymer on the dielectric layer to form a first solid electrolyte
layer containing the electroconductive polymer; and
[0028] carrying out application or impregnation of the
electroconductive polymer suspension on the first solid electrolyte
layer and removing the solvent from the electroconductive polymer
suspension to form a second solid electrolyte layer.
[0029] Also, the electroconductive polymer contained in the first
solid electrolyte layer is preferably a polymer obtained by
chemical oxidative polymerization or electropolymerization of at
least one kind selected from pyrrole, thiophene,
3,4-ethylenedioxythiophene, aniline, and derivatives thereof as a
monomer, and the valve action metal is preferably at least one kind
selected from aluminum, tantalum and niobium.
[0030] According to the present invention, an electroconductive
polymer suspension for providing an electroconductive polymer
material with a high electroconductivity and a method for producing
the same can be provided, and particularly a solid electrolytic
capacitor with a low ESR and a method for producing the same can be
provided.
BRIEF DESCRIPTION OF THE DRAWING
[0031] FIG. 1 is a schematic cross-sectional view showing a
configuration of a solid electrolytic capacitor according to one
embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] The method for producing an electroconductive polymer
suspension of the present invention is explained. In the method for
producing an electroconductive polymer suspension of the present
invention, the first step is to carry out chemical oxidative
polymerization of a monomer providing an electroconductive polymer
by using an oxidant in a solvent containing a first dopant to
synthesize an electroconductive polymer; the second step is to
purify the electroconductive polymer obtained by the first step;
the third step is to add a second dopant, to mix an oxidant, to
subsequently add a third dopant, and to further mix an oxidant in
an aqueous solvent containing the purified electroconductive
polymer; and the fourth step is to carry out an ion-exchange
treatment to the mixture liquid obtained by the third step to
obtain an electroconductive polymer suspension. Further, the fifth
step is to add at least one kind selected from erythritol and
pentaerythritol to the electroconductive polymer suspension
obtained by the fourth step.
[0033] First, as the first step, chemical oxidative polymerization
of a monomer providing an electroconductive polymer by using an
oxidant in a solvent containing a first dopant including an
polysulfonic acid or a salt thereof is carried out to synthesize an
electroconductive polymer. By conducting the first step, an
electroconductive polymer with high polymerization degree and high
crystallinity can be obtained.
[0034] The monomer can appropriately be selected from monomers
providing an electroconductive polymer. Specific examples of the
monomer include pyrrole, thiophene, aniline and derivatives
thereof. Specific examples of the derivative of pyrrole include
3-alkylpyrroles such as 3-hexylpyrrole, 3,4-dialkylpyrroles such as
3,4-dihexylpyrrole, 3-alkoxypyrroles such as 3-methoxypyrrole, and
3,4-dialkoxypyrroles such as 3,4-dimethoxypyrrole. Specific
examples of the derivative of thiophene include
3,4-ethylenedioxythiophene and derivatives thereof,
3-alkylthiophenes such as 3-hexylthiophene, and 3-alkoxythiophenes
such as 3-methoxythiophene. Specific examples of the derivative of
aniline include 2-alkylanilines such as 2-methylaniline, and
2-alkoxyanilines such as 2-methoxyaniline. Among these,
3,4-ethylenedioxythiophene represented by following formula (1) or
a derivative thereof is preferable from the viewpoint of
electroconductivity. Examples of the derivative of
3,4-ethylenedioxythiophene include
3,4-(1-alkyl)ethylenedioxythiophenes such as
3,4-(1-hexyl)ethylenedioxythiophene. The monomer may be used alone,
or in combination with two or more kinds.
##STR00001##
[0035] The concentration of the monomer in the solution is not
particularly limited because the monomer can be removed in the
second step even when it is excessive, however, is preferably 0.5
to 70.0% by mass for obtaining an electroconductive polymer with a
high electroconductivity in good yield, and is more preferably 1.0
to 50.0% by mass.
[0036] As the first dopant, a polysulfonic acid or a salt thereof
is used. Specific examples thereof include polystyrene sulfonic
acids, polyvinyl sulfonic acids, polyester sulfonic acids,
poly(2-acrylamide-2-methylpropane sulfonic acids) and copolymers
having a structural unit thereof. Specific examples of the salt of
polysulfonic acid include lithium salts, sodium salts, potassium
salts, and ammonium salts.
[0037] Among these, polystyrene sulfonic acids having a structural
unit represented by following formula (2) are preferable. The
weight average molecular weight of the polysulfonic acid is
preferably 500000 or less, and is more preferably 200000 or less
for obtaining an electroconductive polymer with a high
electroconductivity. The first dopant may be used alone, or in
combination with two or more kinds.
##STR00002##
[0038] The amount used of the first dopant is not particularly
limited because the first dopant can be removed in the second step
even when it is excessively added, however, is preferably 0.1 to
100.0 parts by mass with respect to 1 part by mass of the monomer
for obtaining an electroconductive polymer with a high
electroconductivity, and is more preferably 0.1 to 20.0 parts by
mass.
[0039] The solvent used for carrying out this reaction is
preferably selected from solvents having a good compatibility with
the monomer, and may be water, an organic solvent or a
water-containing organic solvent. Specific examples of the organic
solvent include alcohol solvents such as methanol, ethanol and
propanol, aromatic hydrocarbon solvents such as benzene, toluene
and xylene, aliphatic hydrocarbon solvents such as hexane, and
aprotic polar solvents such as N,N-dimethylformamide,
dimethylsulfoxide, acetonitrile and acetone. The organic solvent
may be used alone, or in combination with two or more kinds. Among
these, ethanol, or a mixed solvent of ethanol or dimethylsulfoxide
with water is preferable.
[0040] The oxidant is not particularly limited. Examples of the
usable oxidant include iron (III) salts of an inorganic acid such
as iron (III) chloride hexahydrate, anhydrous iron (III) chloride,
iron (III) nitrate nonahydrate, anhydrous ferric nitrate, iron
(III) sulfate n-hydrate (n=3 to 12), ammonium iron (III) sulfate
dodecahydrate, iron (III) perchlorate n-hydrate (n=1, 6) and iron
(III) tetrafluoroborate; copper (II) salts of an inorganic acid
such as copper(II) chloride, copper (II) sulfate and copper (II)
tetrafluoroborate; nitrosonium tetrafluoroborate; persulfates such
as ammonium persulfate, sodium persulfate and potassium persulfate;
periodates such as potassium periodate; hydrogen peroxide, ozone,
potassium hexacyanoferrate (III), tetraammonium cerium (IV) sulfate
dihydrate, bromine and iodine; and iron (III) salts of an organic
acid such as iron (III) p-toluenesulfonate. Among these, the salts
of an inorganic acid or the persulfates are preferable from the
viewpoint of electroconductivity, and ammonium persulfate is more
preferable. The oxidant may be used alone, or in combination with
two or more kinds.
[0041] The amount used of the oxidant is not particularly limited
because the oxidant can be removed by the purification in the
second step even when it is excessively added, however, is
preferably 0.5 to 100.0 parts by mass with respect to 1 part by
mass of the monomer for obtaining an electroconductive polymer with
a high electroconductivity by the reaction under a milder oxidation
atmosphere, and is more preferably 1.0 to 40.0 parts by mass.
[0042] The first step can be conducted in a presence of a
surfactant. Since the monomer has a low solubility to water, the
use of a surfactant in the case where water is used as a solvent
can improve a dispersibility of the monomer. The surfactant may be
an anionic surfactant, a cationic surfactant, an amphoteric
surfactant or a nonionic surfactant, and is preferably dodecyl
benzene sulfonic acid or polyethylene glycol. The surfactant may be
used alone, or in combination with two or more kinds.
[0043] The amount used of the surfactant is not particularly
limited because the surfactant can be removed by the purification
in the second step even when it is excessively added, however, is
preferably 0.01 to 10.0 parts by mass with respect to 1 part by
mass of the monomer, and is more preferably 0.1 to 5.0 parts by
mass.
[0044] The electroconductive polymer obtained by chemical oxidative
polymerization of the monomer has a structural unit derived from
the monomer. For example, in the case where
3,4-ethylenedioxythiophene represented by formula (1) is used as a
monomer, the electroconductive polymer obtained has a structural
unit represented by following formula (3).
##STR00003##
[0045] The chemical oxidative polymerization is preferably carried
out with stirring. The reaction temperature of the chemical
oxidative polymerization is not particularly limited, but the upper
limit may be a reflux temperature of the solvent used. It is
preferably 0 to 100.degree. C., and is more preferably 10 to
50.degree. C. If the reaction temperature is not proper, the
electroconductivity of the electroconductive polymer obtained may
be lowered. The reaction time of the chemical oxidative
polymerization depends on the kind and the amount used of the
oxidant, the reaction temperature and the stirring condition, but
it is preferably approximately 5 to 100 hours. When an
electroconductive polymer is formed, the color of the reaction
liquid is changed to dark blue.
[0046] Next, as the second step, the electroconductive polymer is
purified. Concretely, the electroconductive polymer is separated
from a reaction liquid containing the electroconductive polymer
obtained by chemical oxidative polymerization and is washed to
remove the dopant, the monomer, the oxidant and the reacted
oxidant. By conducting the second step, an electroconductive
polymer with high purity can be obtained. Examples of the method
for separating the electroconductive polymer from the reaction
liquid include filtration method and centrifugal method.
[0047] The washing solvent used in the second step is preferably a
solvent in which the electroconductive polymer is not dissolved and
the monomer and/or the oxidant can be dissolved. Specific examples
of the washing solvent include water and alcohol solvents such as
methanol, ethanol and propanol. The washing solvent may be used
alone, or in combination with two or more kinds. The extent of
washing can be confirmed by measuring the pH of the washing solvent
after washing or by carrying out colorimetric observation by using
an examination reagent or the like.
[0048] Further, since it is possible to remove a metal component
derived from the oxidant, a halogen and a sulfuric acid component
more highly, it is preferable to wash the electroconductive polymer
with hot water and/or to wash it with an organic solvent and/or to
heat treat it. The organic solvent is preferably dimethylsulfoxide,
N,N-dimethylformamide, dimethylacetamide or the like. The
temperature of the heat treatment is not particularly limited as
long as it is equal to or lower than the decomposition temperature
of the electroconductive polymer, but it is preferably lower than
300.degree. C. Also, it is efficient as a method for removing a
component derived from the oxidant to carrying out a known
ion-exchange treatment by using an ion exchange resin. The impurity
contained in the electroconductive polymer can be analyzed by
atomic absorption method analysis, ICP emission analysis, ion
chromatography or the like.
[0049] Then, in the third step, the purified electroconductive
polymers are dispersed in an aqueous solvent, and an aqueous
solution containing a polyacid component as a second dopant is
added, and an oxidant is mixed. After that, an organic acid with a
low molecular weight or a salt thereof as a third dopant is added,
and an oxidant is mixed to obtain an electroconductive polymer
suspension.
[0050] Since the polyacid functions as a dispersing agent in the
third step, an electroconductive polymer suspension with good
dispersibility can be obtained. As a dispersing mechanism, at least
a doping effect of a polyanion derived from the polyacid component
is considered.
[0051] The aqueous solvent is preferably water and may be a mixed
solvent of water and a water-soluble organic solvent. Specific
examples of the water-soluble organic solvent include protic polar
solvents such as methanol, ethanol, propanol, and acetic acid, and
aprotic polar solvents such as N,N-dimethylformamide,
dimethylsulfoxide, acetonitrile and acetone.
[0052] The concentration of the electroconductive polymer in the
aqueous solvent is preferably 0.1 to 20.0% by mass for improving
the dispersibility, and is more preferably 0.5 to 10.0% by
mass.
[0053] A polyacid or a salt thereof can be used as the polyacid
component that is a second dopant. Specific examples of the
polyacid include polycarboxylic acids such as polyacrylic acids,
polymethacrylic acids and polymaleic acids, polysulfonic acids such
as polyvinyl sulfonic acids,
poly(2-acrylamide-2-methylpropanesulfonic acid) and polystyrene
sulfonic acids, and copolymers having a structural unit thereof.
Specific examples of the salt of the polyacid include lithium
salts, sodium salts, potassium salts and ammonium salts of the
polyacids. Among these, polystyrene sulfonic acids having a
structural unit represented by formula (2) are preferable. The
polyacid component may be used alone, or in combination with two or
more kinds.
[0054] The weight average molecular weight of the polyacid
component is preferably 2000 to 500000 for obtaining an
electroconductive polymer with a high electroconductivity, and is
more preferably 10000 to 200000.
[0055] The amount used of the polyacid component is preferably 20
to 3000 parts by mass with respect to 100 parts by mass of the
electroconductive polymer for obtaining an electroconductive
polymer with a high electroconductivity, and is more preferably 20
to 1000 parts by mass.
[0056] Further, by adding the organic acid with a low molecular
weight or the salt thereof as a third dopant and by mixing the
oxidant, a dope rate of the electroconductive polymer can be
improved. This is presumed to be because the molecular weight of
the organic acid with a low molecular weight or the salt thereof is
lower than that of the polyacid component and thereby the dope rate
of the electroconductive polymer is raised and the
electroconductivity can be improved.
[0057] Specific examples of the organic acid with a low molecular
weight or the salt thereof include benzenesulfonic acid,
naphthalenesulfonic acid, anthraquinonesulfonic acid,
camphorsulfonic acid, alkyl sulfonic acids and derivatives thereof
and iron (Ill) salts thereof. Also, the organic acid with a low
molecular weight may be a monosulfonic acid, disulfonic acid and
trisulfonic acid. Specific examples of the derivative of the alkyl
sulfonic acid include 2-acrylamide-2-methylpropanesulfonic
acid.
[0058] Specific examples of the derivative of benzenesulfonic acid
include phenolsulfonic acid, styrenesulfonic acid, toluenesulfonic
acid, and dodecyl benzene sulfonic acid. Specific examples of the
derivative of naphthalenesulfonic acid include
1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid,
1,3-naphthalenedisulfonic acid, 1,3,6-naphthalenetrisulfonic acid
and 6-ethyl-1-naphthalenesulfonic acid. Specific examples of the
derivative of anthraquinonesulfonic acid include
anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid,
anthraquinone-2,6-disulfonic acid and
2-methylanthraquinone-6-sulfonic acid. Among these,
1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid,
1,3,6-naphthalenetrisulfonic acid, anthraquinonedisulfonic acid,
p-toluenesulfonic acid, camphorsulfonic acid or the iron (III)
salts thereof are preferable.
[0059] Further, from the point of improving the
electroconductivity, naphthalenesulfonic acid is preferable, and
2-naphthalenesulfonic acid is particularly preferable. The organic
acid with a low molecular weight or the salt thereof may be used
alone, or in combination with two or more kinds.
[0060] As the oxidant in the third step, the same oxidant in the
first step can be used. Among these, ammonium persulfate or
hydrogen peroxide is preferable. The amount used of the oxidant is
preferably 0.5 to 50.0 parts by mass with respect to 1 part by mass
of the electroconductive polymer obtained by the second step for
obtaining an electroconductive polymer with a high
electroconductivity, and is more preferably 1.0 to 30.0 parts by
mass.
[0061] The reaction temperature of the third step is not
particularly limited, but is preferably in a range of 0.degree. C.
to 100.degree. C., and is more preferably 10.degree. C. to
50.degree. C. The reaction time of the third step is not
particularly limited, but is approximately 5 to 100 hours.
[0062] Further, as the fourth step, the above-mentioned
ion-exchange treatment is carried out after the third step. By
carrying out the ion-exchange treatment, a residual ion component
such as sulfuric acid ion which is derived from the oxidant can be
removed. Also, by carrying out the ion-exchange treatment, it is
possible to improve the film forming property of the
electroconductive polymer when the electroconductive polymer
suspension is dried and the solvent is removed. Of course, it is
possible to substitute a well-known treatment step which
corresponds to this.
[0063] It is preferable to conduct a fifth step of mixing at least
one kind selected from erythritol and pentaerythritol after the
fourth step. By conducting the fifth step, it is possible to
realize a further higher electroconductivity because it interacts
with the polyacid component (undoped dopant anion (resistance
component)) which exists in the vicinity of the electroconductive
polymers in the electroconductive polymer suspension, and thereby
the resistance between the electroconductive polymer particles is
lowered and the density of the electroconductive polymer is
increased.
[0064] Erythritol is preferable because it has a higher
crystallinity than, for example, those of polyols such as sorbitol
and maltose, and thereby has a low hygroscopicity and is easy to be
handled. Also, erythritol is known as a food additive used as a
sweetener, and is excellent in safety and stability. Further,
erythritol is several-fold higher in the solubility to water than,
for example, non-aqueous solvent such as ethylene glycol and
glycerin, and provides an advantage that there is a lot of
flexibility in designing the addition amount thereof.
[0065] Pentaerythritol is characterized by being slowly sublimed
when heated, and by being dehydrated and polymerized by the heating
at a temperature equal to or higher than the melting point thereof.
Thereby, pentaerythritol has an advantage that the properties of
the organic material are changed to improve the density and the
strength thereof. Such reactivity originates from the chemical
structure thereof, and hardly results from the chemical structure
such as that of erythritol or sorbitol.
[0066] A larger advantageous effect is realized by mixing
erythritol or pentaerythritol in an amount so that the
concentration of erythritol or pentaerythritol comes to be equal to
or higher than that the concentration of the electroconductive
polymer in the electroconductive polymer suspension. The upper
limit of the mixing amount is not particularly limited as long as
it can be dissolved in the electroconductive polymer
suspension.
[0067] A resin which functions as a binding action may be added to
the electroconductive polymer suspension obtained. Specific
examples of this resin include polyester resins, polyethylene
resins, polyamide resins, polyimide resins, polyether resins and
polystyrene resins. The amount added of this resin is preferably
0.01 to 20 parts by mass with respect to 100 parts by mass of the
electroconductive polymer suspension from the viewpoint of keeping
the electroconductivity.
[0068] The electroconductive polymer suspension of the present
invention is usually dark blue.
[0069] An electroconductive polymer material can be obtained by
removing the solvent from the electroconductive polymer suspension
of the present invention. This electroconductive polymer material
has a high electroconductivity. Since this electroconductive
polymer material has a high crystallinity of the electroconductive
polymer and disperses light, it has no transparency and exhibits a
color near black.
[0070] The removal of the solvent can be carried out by drying the
electroconductive polymer suspension. The temperature of the drying
is not particularly limited as long as it is equal to or lower than
the decomposition temperature of the electroconductive polymer, but
it is preferably 300.degree. C. or lower.
[0071] Further, the electroconductive polymer material obtained by
removing the solvent from the electroconductive polymer suspension
of the present invention also has a property of low moisture
absorbency. It is thought that it is caused by esterifying the
undoped sulfonic acid group that is the polyacid in the
electroconductive polymer suspension, erythritol and
pentaerythritol during drying, resulting that the hydrophilic group
disappears.
[0072] Also, the electroconductive polymer material obtained by
removing the solvent from the electroconductive polymer suspension
of the present invention can be used as a solid electrolyte layer
of a solid electrolytic capacitor. Since the electroconductive
polymer contained in the electroconductive polymer suspension or
the electroconductive polymer material obtained by removing the
solvent from the electroconductive polymer suspension has a high
electroconductivity, a condenser with a low ESR can be obtained.
Further, since the electroconductive polymer has a high
crystallinity, the oxygen barrier property is also high associated
with it and the improvement of the reliability of the condenser is
also sufficiently anticipated.
[0073] Next, a configuration of a solid electrolytic capacitor
using the electroconductive polymer material obtained from the
electroconductive polymer suspension and a production method is
explained by using drawings. FIG. 1 is a schematic cross-sectional
view showing a configuration of a solid electrolytic capacitor
according to one embodiment of the present invention.
[0074] This solid electrolytic capacitor has a configuration in
which dielectric layer 2, solid electrolyte layer 3 and cathode
conductor 4 are formed in this order on anode conductor 1.
[0075] Anode conductor 1 is formed of: a plate, a foil or a wire of
a valve action metal; a sintered body containing fine particles of
a valve action metal; a porous metal subjected to a surface area
enlargement treatment by etching; or the like. Specific examples of
the valve action metal include tantalum, aluminum, titanium,
niobium and zirconium, and alloys thereof. Among these, at least
one valve action metal selected from aluminum, tantalum and niobium
is preferable.
[0076] Dielectric layer 2 is a layer which can be formed by
electrolytic oxidation of the surface of anode conductor 1, and is
also formed in the pores of a sintered body or a porous body. The
thickness of dielectric layer 2 can be appropriately adjusted by
the voltage of the electrolytic oxidation.
[0077] Solid electrolyte layer 3 contains the electroconductive
polymer material obtained by removing the solvent from the
above-mentioned electroconductive polymer suspension. Examples of
the method for forming solid electrolyte layer 3 include a method
of application or impregnation of the above-mentioned
electroconductive polymer suspension on dielectric layer 2, and of
removing the solvent from the electroconductive polymer suspension
The method of application or impregnation method is not
particularly limited. However, in order to sufficiently fill the
electroconductive polymer suspension in the interior of the pores
of the porous material, it preferably leaves for a few minutes to a
few tens of minutes after application or impregnation. It is
preferable to repeat immersion or to operate it under a
circumstance of a pressure reduced from atmospheric pressure or
under a circumstance of an increased pressure.
[0078] The removal of the solvent from the electroconductive
polymer suspension can be carried out by drying the
electroconductive polymer. The temperature of the drying is not
particularly limited as long as it is within a temperature range in
which the solvent can be removed. However, from the viewpoint of
preventing the degradation of the element by a heat, the upper
limit of the temperature is preferably lower than 300.degree. C. It
is necessary to appropriately optimize the time of the drying
according to the temperature of the drying, but it is not
particularly limited as long as it is within a range in which the
electroconductivity is kept.
[0079] Further, it may contain an electroconductive polymer
containing pyrrole, thiophene, aniline or a derivative thereof, an
oxide derivative such as manganese dioxide or ruthenium oxide, or
an organic semiconductor such as TCNQ
(7,7,8,8-tetracyanoquinodimethane complex salt).
[0080] For example, solid electrolyte layer 3 can be designed to
have a two-layer structure of first solid electrolyte layer 3a and
second solid electrolyte layer 3b. And, chemical oxidative
polymerization or electropolymerization of a monomer providing an
electroconductive polymer on dielectric layer 2 is carried out to
form first solid electrolyte layer 3a containing the
electroconductive polymer. Application or impregnation of the
above-mentioned electroconductive polymer suspension on first solid
electrolyte layer 3a is carried out and the solvent is removed from
the electroconductive polymer suspension to form second solid
electrolyte layer 3b.
[0081] As a monomer, at least one kind selected from pyrrole,
thiophene, aniline and derivatives thereof can be used. As a dopant
used for chemical oxidative polymerization or the
electropolymerization of the monomer to obtain an electroconductive
polymer, sulfonic acid compounds such as alkyl sulfonic acids,
benzenesulfonic acid, naphthalenesulfonic acid,
anthraquinonesulfonic acid, camphorsulfonic acid and the
derivatives thereof are preferable. The molecular weight of the
dopant used can be appropriately selected from low molecular weight
compounds to high molecular weight compounds. The solvent may be
water only or may also be a mixed solvent of water and a
water-soluble organic solvent.
[0082] It is preferable that the electroconductive polymer which is
contained in first solid electrolyte layer 3a and the
electroconductive polymer which is contained in second solid
electrolyte layer 3b contain at least the same polymer.
[0083] Cathode conductor 4 is not particularly limited as long as
it is a conductor. For example, it can be designed to have a
two-layer structure formed of graphite layer 4a and silver
electroconductive resin layer 4b.
EXAMPLES
[0084] As follows, the Examples of the present invention are
concretely explained.
Example 1
(First Step)
[0085] 1 g of 3,4-ethylenedioxythiophene as a monomer and 6 g of
20% aqueous solution of a polystyrene sulfonic acid (weight average
molecular weight: 50000) as a first dopant were added to 100 mL of
an ethanol aqueous solution, and it was stirred at room temperature
for 30 minutes.
[0086] Then, 4.2 ml of 30% aqueous solution of ammonium persulfate
as an oxidant was added thereto in 5 parts of the same amount every
10 minutes. After that, it was stirred at room temperature for 50
hours to carry out chemical oxidative polymerization and a
polythiophene (3,4-ethylenedioxythiophene) was synthesized. During
this, the color of the solution was changed from yellow via light
green, green and light navy blue to black.
(Second Step)
[0087] The solution obtained was filtered by using a pressure
reduction filtration equipment to collect a powder. The powder was
washed with pure water to remove the excessive oxidant and the
excessive dopant. The washing with pure water was repeated until
the acidity of the filtrate came to be a pH of 6 to 7. After that,
the powder was further washed with ethanol to remove the monomer.
The washing with ethanol was carried out until the filtrate came to
be colorless and transparent. At this time, the powder exhibited
dark blue. Further, after the washing, it was heated in a
thermostatic oven at 125.degree. C.
(Third Step)
[0088] 0.5 g of the powder after purification was dispersed in 50
ml of water and then 1.9 g of an aqueous solution containing a
polystyrene sulfonic acid (weight average molecular weight: 50000)
in 20% by mass which was a polyacid component as a second dopant
was added thereto. 1.5 g of ammonium persulfate as an oxidant was
added thereto and it was stirred at room temperature for 50 hours.
Further, 1.0 g of 2-naphthalenesulfonic acid which was an organic
acid with a low molecular weight as a third dopant was added, and
1.0 g of ammonium persulfate as an oxidant was added. After that,
it was stirred under room temperature for 10 hours. The
polythiophene suspension obtained was dark navy blue.
(Fourth Step)
[0089] 5 g of an amphoteric ion-exchange resin (product name: MB-1,
ion-exchange type: --H and --OH, made by ORGANO CORPORATION) was
mixed with 10 g of the polythiophene suspension obtained, and it
was stirred under room temperature for 1 hour. This resulted in
removing sulfate ion derived from the oxidant. Here, as compared to
pH before the mixing with the ion exchange resin, it was confirmed
to rise approximately 1 of pH.
[0090] The polythiophene suspension obtained was dropped onto a
glass substrate in an amount of 100 .mu.l and was dried in a
thermostatic oven at 150.degree. C. to form an electroconductive
polymer film including an electroconductive polymer material. The
surface resistance (QC) and the film thickness of the
electroconductive polymer film were measured by four-terminal
method to calculate the electroconductivity (S/cm) of the
electroconductive polymer film. The result is shown in TABLE 1.
Example 2
[0091] A polythiophene suspension was produced by the same method
as that of Example 1 except that 3.0 g of 2-naphthalenesulfonic
acid was added as a third dopant. Further, an electroconductive
polymer film was formed by the same method as that of Example 1,
and the electroconductivity of the electroconductive polymer film
was calculated. The result is shown in TABLE 1.
Example 3
[0092] A polythiophene suspension was produced by the same method
as that of Example 1 except that 1.0 g of p-toluenesulfonic acid
was added as a third dopant. Further, an electroconductive polymer
film was formed by the same method as that of Example 1, and the
electroconductivity of the electroconductive polymer film was
calculated. The result is shown in TABLE 1.
Example 4
[0093] A polythiophene suspension was produced by the same method
as that of Example 1 except that 1.0 g of dodecylbenzenesulfonic
acid was added as a third dopant. Further, an electroconductive
polymer film was formed by the same method as that of Example 1,
and the electroconductivity of the electroconductive polymer film
was calculated. The result is shown in TABLE 1.
Example 5
[0094] A polythiophene suspension was produced by further
dissolving 1 g of erythritol in 10 g of the polythiophene
suspension obtained in Example 1 at room temperature. And, an
electroconductive polymer film was formed by the same method as
that of Example 1, and the electroconductivity of the
electroconductive polymer film was calculated, The result is shown
in TABLE 1.
Example 6
[0095] A polythiophene suspension was produced by further
dissolving 0.5 g of pentaerythritol in 10 g of the polythiophene
suspension obtained in Example 5 at room temperature. And, an
electroconductive polymer film was formed by the same method as
that of Example 1, and the electroconductivity of the
electroconductive polymer film was calculated. The result is shown
in TABLE 1.
Comparative Example 1
[0096] A polythiophene suspension was produced by the same method
as that of Example 1 except that the third dopant and the oxidant
were not added in third step. And, an electroconductive polymer
film was formed by the same method as that of Example 1, and the
electroconductivity of the electroconductive polymer film was
calculated. The result is shown in TABLE 1.
Comparative Example 2
[0097] As an example of a conventional synthesis method of a
suspension, 2.0 g of polystyrene sulfonic acid (weight average
molecular weight: 50000), 0.5 g of 3,4-ethylenedioxythiophene and
0.05 g of iron (Ill) sulfate were dissolved in 20 ml of water and
air was introduced for 24 hours to produce a polythiophene
suspension. And, an electroconductive polymer film was formed by
the same method as that of Example 1, and the electroconductivity
of the electroconductive polymer film was calculated. The result is
shown in TABLE 1.
Example 7
[0098] Porous aluminum was used as an anode conductor including a
valve action metal, and an oxide coating film was formed on the
surface of the aluminum metal by anodic oxidation. Then, the anode
conductor having the dielectric layer formed was immersed in and
taken out from a monomer liquid, in which 10 g of pyrrole as a
monomer was dissolved in 200 ml of pure water, and was immersed in
and taken out from an oxidant liquid, in which 20 g of
p-toluenesulfonic acid as a dopant and 10 g of ammonium persulfate
as an oxidant were dissolved in 200 ml of pure water, in this
order. These operations were repeated 10 times. A chemical
oxidative polymerization was carried out to form a first solid
electrolyte layer.
[0099] The polythiophene suspension produced in Example 1 was
dropped onto the first solid electrolyte layer, and it was dried
and solidified at 165.degree. C. to form a second solid electrolyte
layer. On the second solid electrolyte layer, a graphite layer and
a silver-containing resin layer were formed in this order to obtain
a solid electrolytic capacitor. The ESR of the solid electrolytic
capacitor obtained was measured by using an LCR meter at a
frequency of 100 kHz. The ESR value was normalized from the value
of the total cathode area to the value of the unit area (1
cm.sup.2). The result is shown in TABLE 2.
Example 8
[0100] A solid electrolytic capacitor was produced by the same
method as that of Example 7 except that a second solid electrolyte
layer was formed by using the polythiophene suspension produced in
Example 6. The result of ESR measured by the same method as that of
Example 7 is shown in TABLE 2.
Comparative Example 3
[0101] A solid electrolytic capacitor was produced by the same
method as that of Example 7 except that a second solid electrolyte
layer was formed by using the polythiophene suspension produced in
Comparative Example 1. The result of ESR measured by the same
method as that of Example 7 is shown in TABLE 2.
Comparative Example 4
[0102] A solid electrolytic capacitor was produced by the same
method as that of Example 7 except that a second solid electrolyte
layer was formed by using the polythiophene suspension produced in
Comparative Example 2. The result of ESR measured by the same
method as that of Example 7 is shown in TABLE 2.
TABLE-US-00001 TABLE 1 electroconductivity Examples (S/cm) Example
1 200 Example 2 150 Example 3 180 Example 4 170 Example 5 280
Example 6 300 Comparative Example 1 110 Comparative Example 2
60
TABLE-US-00002 TABLE 2 Examples ESR (m.OMEGA. cm.sup.2) Example 7
2.0 Example 8 1.5 Comparative Example 3 2.5 Comparative Example 4
3.0
[0103] As shown in TABLE 1, the electroconductive polymer films
obtained in Examples 1 to 4 had a higher electroconductivity than
those obtained in Comparative Examples 1 and 2. The addition of the
organic acid with a low molecular weight that is a third dopant in
the third step is thought to result in the improvement of the dope
rate in the electroconductive polymer. By these, the advantageous
effect of the present invention could be confirmed.
[0104] Also, the electroconductive polymer films obtained in
Examples 5 and 6 had a further higher electroconductivity than
those obtained in Examples 1 to 4. It was thought that the addition
of the fifth step enables the removal of an undoped polyacid
component and results in decreasing the resistance between
electroconductive polymer particles and increasing the density of
the electroconductive polymer, and that the electroconductive
polymer material with a high electroconductivity could be
obtained.
[0105] Also, as shown in TABLE 2, the solid electrolytic capacitors
obtained in Examples 7 and 8 had a lower ESR than those obtained in
Comparative Examples 3 and 4. By these, the advantageous effect of
the present invention could be confirmed.
[0106] The embodiment of this invention was explained by using the
Examples in the above, but this invention is not limited to these
Examples and includes an embodiment after a design variation within
a scope of this invention. That is, this invention includes an
embodiment after various changings or modifications which can be
made by a person ordinarily skilled in the art.
* * * * *